Sol–gel synthesis and characterization of fluoride-rich lanthanum-alumino-silicate gels doped with Ce3+ and Ti4+

• Lanthanum-alumino-silicate gels with high fluorine content are synthesized.
• Trifluoroacetic acid (TFA) is used as the fluorine source in a sol–gel process.
• Thermal decomposition of TFA prevents the conversion of gels to monolithic glasses.
• The Ce-doped gels show photoluminescence in the blue spectral region.

A series of lanthanum-alumino-silicate gels doped with Ce3+ (0.5–10.0 mol%) and Ti4+ were synthesized by a sol–gel process using trifluoroacetic acid (TFA) as a fluorine source. The structural (X-ray diffraction, scanning electron microscopy), thermal (differential scanning calorimetry), and optical (absorption, photoluminescence, photoluminescence-excitation) properties were investigated. A high fluorine content of up to 22.3 at.% was measured in the dried gels, significantly exceeding the ⩽5 at.% fluorine content of earlier studies. The monolithic gels were transparent, amorphous, and stable up to 250–300 °C. However, the gels lost their structural integrity at temperatures above 315 °C due to the thermal decomposition of TFA. The sol–gel route using TFA as a fluorine source is therefore not a viable route for the preparation of nanostructured glass ceramics containing a high volume fraction of crystalline LnF3. All Ce3+-doped gels showed luminescence in the blue spectral region. Gels containing Ti4+ had an additional strong oxygen-to-metal charge transfer transition that competed with the Ce3+ optical excitation and led to overall lower emission intensity. The measured luminescence intensity of all gel compositions decreased with increasing Ce3+ concentration as a result of increased reabsorption of Ce3+ emission by other Ce3+ ions in the gel as well as energy migration among Ce3+ ions to quenching sites.